Fluorescence imaging assisted by surface modes on dielectric multilayers

The scaling behavior of criticality for spin-1 XXZ chains with uniaxial single-ion-type anisotropy is investigated by employing the infinite matrix product state representation with the infinite time evolving block decimation method. At criticality, the accuracy of the ground state of a system is limited by the truncation dimension χ of the local Hilbert space. We present four evidences for the scaling of the entanglement entropy, the largest eigenvalue of the Schmidt decomposition, the correlation length, and the connection between the actual correlation length ξ and the energy. The result shows that the finite scalings are governed by the central charge of the critical system. Also, it demonstrates that the infinite time evolving block decimation algorithm by the infinite matrix product state representation can be a quite accurate method to simulate the critical properties at criticality.     

A Study on the Optically Active Polymer Poly‐β‐pinene

Poly‐β‐pinene (PBP) was obtained by radiation‐induced polymerization of monomer with γ radiation. The polymerizations were conducted both in vacuum and in the presence of air at different radiation doses up to 1–3 MGy. It was found that the presence of oxygen retards the polymerization rate and reduces the polymer yields and the radiation chemical yield suggesting that the polymerization mechanism involves free radicals. It is shown that PBP can also be obtained in low yields from β‐(‐)pinene polymerization with a free radical initiator. The chemical structures of the PBP radiopolymer and PBP obtained by a free radical initiator were studied by FT‐IR and ¹³C CP‐MAS NMR spectroscopy. The data shows that the PBP obtained have highly ordered structures, which is manifested also by the very high specific optical rotation which is about 3 times that of the starting monomer in the case of the radiopolymer and about 5 times in the case of the PBP prepared with the free radical initiator. In contrast, PBP obtained in high yields by cationic polymerization shows a very low specific optical rotation, much lower than that of the starting monomer and low regularity in chemical structure has been attributed to this polymer by FT‐IR and ¹³C CP‐MAS NMR spectroscopy. It is shown that PBP with high optical activity racemizes over an acidic catalyst.     

Factors affecting drug adsorption on beta zeolites

The adsorption behaviour of three commonly used drugs, namely ketoprofen, hydrochlorothiazide and atenolol, from diluted aqueous solutions on beta zeolites with different SiO₂/Al₂O₃ ratio (i.e. 25, 38 and 360) was investigated by changing the ionic strength and the pH, before and after thermal treatment of the adsorbents. The selective adsorption of drugs was confirmed by thermogravimetry and X‐ray diffraction. The adsorption capacity of beta zeolites was strongly dependent on both the solution pH and the alumina content of the adsorbent. Such a remarkable difference was interpreted as a function of the interactions between drug molecules and zeolite surface functional groups. Atenolol was readily adsorbed on the less hydrophobic zeolite, under pH conditions in which electrostatic interactions were predominant. On the other hand, ketoprofen adsorption was mainly driven by hydrophobic interactions. For undissociated molecules the adsorption capability increased with the increase of hydrophobicity.     

Comparative analysis of commercial dermal fillers based on crosslinked hyaluronan: Physical characterization and in vitro enzymatic degradation

The cosmetic market for hyaluronic acid (HA)-based dermal fillers is in continuous and rapid growth and, simultaneously, the development of more effective and safer products is strongly intensifying. In order to highlight the differences among the currently available fillers, in terms of their physical characteristics and on the relation of such properties with product effectiveness, an in vitro evaluation of eight marketed HA-based gels was performed.Filler swelling properties, soluble HA fraction and rheological behaviour were investigated. Furthermore the relative stability to enzymatic hydrolysis was tested. The presence of soluble HA in the formulations varied from 7 ± 1(%) to 33 ± 5(%) with respect to the total HA concentration. Chromatographic analyses showed that the soluble fractions consist of low molecular weight chains (M_w: 260-480 kDa) presenting large distributions (M_w/M_n: 1.6-2.5). The investigated fillers were found to be non-equilibrium gels in their commercial formulation also showing different swelling capacities. Rheological measurements indicated a shear thinning behaviour for all the products and elastic modulus values varied over a wide range (100-1800 Pa). Fillers proved differently sensitive to enzymatic degradation. Swelling capacity and enzymatic stability were found consistently dependent on the total HA concentration, insoluble/soluble HA ratio and on the crosslinking extent.     

Spectroscopic investigation and molecular modeling on porphyrin/PAMAM supramolecular adduct

Noncovalent adducts (TPPC@PAMAM) between meso-tetrakis(4-carboxyphenyl)porphyrin (TPPC) and polyamidoamine PAMAM dendrimer (generation 2.0) have been obtained by simply mixing the two components at different stoichiometric amount. The resulting species are readily soluble and stable in aqueous solution up to millimolar concentration. Electrostatic interactions between the anionic carboxylate groups of TPPC and the protonated amino groups of the PAMAM dendrimer play an important role in the stabilization of these adducts. UV/Vis absorption, steady state and time-resolved fluorescence emission and anisotropy measurements suggest the presence of equilibria involving different species as function of the [PAMAM]/[TPPC] ratio. At low ratios the observed spectroscopic behavior evidence the presence of H-aggregates, while at higher ratios well-defined species containing monomeric TPPC strongly interacting with the charged dendrimer are formed. Docking of the binary supramolecular adduct further supports the experimental results showing a favorable interaction with the porphyrin being completely included in the dendrimer. The interaction of the binary TPPC@PAMAM adduct (1/1 ratio) with calf-thymus DNA has been investigated through spectroscopic and photophysical techniques. All the experimental results point to the formation of a ternary complex between the binary adduct and the DNA backbone.     

A new non-destructive method for chemical analysis of particulate matter filters: the case of manganese air pollution in Vallecamonica (Italy)

Total Reflection X-ray Fluorescence (TXRF) is a well-established technique for chemical analysis, but it is mainly employed for quality control in the electronics semiconductor industry. The capability to analyze liquid and uniformly thin solid samples makes this technique suitable for other applications, and especially in the very critical field of environmental analysis. Comparison with standard methods like inductively coupled plasma (ICP) and atomic absorption spectroscopy (AAS) shows that TXRF is a practical, accurate, and reliable technique in occupational settings. Due to the greater sensitivity necessary in trace heavy metal detection, TXRF is also suitable for environmental chemical analysis. In this paper we show that based on appropriate standards, TXRF can be considered for non-destructive routine quantitative analysis of environmental matrices such as air filters. This work has been developed in the frame of the EU-FP6 PHIME (Public Health Impact of long-term, low-level Mixed element Exposure in susceptible population strata) Integrated Project (www.phime.org). The aim of this work was to investigate Mn air pollution in the area of Vallecamonica (Italy).     

Patterned deposition by plasma enhanced spatial atomic layer deposition

An atmospheric pressure plasma enhanced atomic layer deposition reactor has been developed, to deposit Al₂O₃ films from trimethyl aluminum and an He/O₂ plasma. This technique can be used for 2D patterned deposition in a single in‐line process by making use of switched localized plasma sources. It was observed that the sharpness of the patterns is primarily influenced by the concentration of reactive plasma species and by the dimensions of the plasma source. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Shapes of Sulfonamides: A Rotational Spectroscopy Study

Benzenesulfonamides are a class of molecules of extreme interest in the biochemical field because many of them are active against a variety of diseases. In this work, the pharmacophoric group benzensulfonamide, its derivatives para-toluensulfonamide and ortho-toluensulfonamide, and the bioactive molecule sulfanilamide, were investigated using rotational spectroscopy to determine their conformations and the influence of different substituents on their structures. For all species, the hyperfine structure due to the ¹⁴N atom was analyzed, and this provided crucial information for the unambiguous identification of the observed conformation of all molecules. In addition, for ortho-toluensulfonamide, the vibration–rotation hyperfine structure related to the methyl torsion was analyzed, and the methyl group rotation barrier was determined. For benzensulfonamide, partial r_S and r₀ structures were established from the experimental rotational constants of the parent and two deuterated isotopic species. In all compounds except ortho-toluensulfonamide, the amino group of the sulfonamide group lies perpendicular to the benzene plane with the aminic hydrogens eclipsing the oxygen atoms. In ortho-toluensulfonamide, where weak attractive interactions occur between the nitrogen lone pair and the methyl hydrogen atoms, the amino group lies in a gauche orientation, retaining the eclipsed configuration with respect to the SO₂ frame. A comparison of the geometrical arrangements found in the PDB database allowed us to understand that the bioactive conformations are different from those found in isolated conditions. The conformations within the receptor are reached with an energy cost, which is balanced by the interactions established in the receptor.     

First Evidence of Anti-Steatotic Action of Macrotympanain A1, an Amphibian Skin Peptide from Odorrana macrotympana

Many different amphibian skin peptides have been characterized and proven to exert various biological actions, such as wound-healing, immunomodulatory, anti-oxidant, anti-inflammatory and anti-diabetic effects. In this work, the possible anti-steatotic effect of macrotympanain A1 (MA1) (FLPGLECVW), a skin peptide isolated from the Chinese odorous frog Odorrana macrotympana, was investigated. We used a well-established in vitro model of hepatic steatosis, consisting of lipid-loaded rat hepatoma FaO cells. In this model, a 24 h treatment with 10 µg/mL MA1 exerted a significant anti-steatotic action, being able to reduce intracellular triglyceride content. Accordingly, the number and diameter of cytosolic lipid droplets (LDs) were reduced by peptide treatment. The expression of key genes of hepatic lipid metabolism, such as PPARs and PLINs, was measured by real-time qPCR. MA1 counteracted the fatty acid-induced upregulation of PPARγ expression and increased PLIN3 expression, suggesting a role in promoting lipophagy. The present data demonstrate for the first time a direct anti-steatotic effect of a peptide from amphibian skin secretion and pave the way to further studies on the use of amphibian peptides for beneficial actions against metabolic diseases.     

Native mass spectrometric studies of IscSU reveal a concerted,sulfur-initiated mechanism of iron–sulfur cluster assembly

Iron–sulfur (Fe–S) clusters are cofactors essential for life. Though the proteins that function in the assembly of Fe–S clusters are well known, details of the molecular mechanism are less well established. The Isc (iron–sulfur cluster) biogenesis apparatus is widespread in bacteria and is the closest homologue to the human system. Mutations in certain components of the human system lead to disease, and so further studies of this system could be important for developing strategies for medical treatments. We have studied two core components of the Isc biogenesis system: IscS, a cysteine desulfurase; and IscU, a scaffold protein on which clusters are built before subsequent transfer onto recipient apo-proteins. Fe²⁺-binding, sulfur transfer, and formation of a [2Fe–2S] was followed by a range of techniques, including time-resolved mass spectrometry, and intermediate and product species were unambiguously identified through isotopic substitution experiments using ⁵⁷Fe and ³⁴S. Under cluster synthesis conditions, sulfur adducts and the [2Fe–2S] cluster product readily accumulated on IscU, but iron adducts (other than the cluster itself) were not observed at physiologically relevant Fe²⁺ concentrations. Our data indicate that either Fe²⁺ or sulfur transfer can occur first, but that the transfer of sulfane sulfur (S⁰) to IscU must occur first if Zn²⁺ is bound to IscU, suggesting that it is the key step that initiates cluster assembly. Following this, [2Fe–2S] cluster formation is a largely concerted reaction once Fe²⁺ is introduced.

Time-resolved native mass spectrometry was used to investigate iron–sulfur cluster assembly on IscU. Data revealed a concerted assembly process in which sulfur (S⁰) transfer must occur first if IscU is in its Zn²⁺-bound form.